Herbicidal sulfonamides

ABSTRACT

This invention relates to novel sulfonamides, agriculturally suitable compositions containing them and their method-of-use as selective pre-emergent or post-emergent herbicides.

RELATED APPLICATIONS

This application is a continuation-in-part of my copending applicationU.S. Ser. No. 392,364, filed Mar. 24, 1983 now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to novelN-(heterocyclicaminocarbonyl)arylsulfonamides in which the aryl radicalis substituted with a carboxyl radical. The compounds of this inventionand their agriculturally suitable salts, are useful as agriculturalchemicals, herbicides which may be selective and regulate growth.

In EPO Publication No. 7,687, there is disclosed herbicidal compounds ofthe general formula within the broad generic scope. ##STR1## wherein

R may be C₁ -C₁₂ alkyl;

R₂ and R₃ may be hydrogen, as may R₄ and R₅ ;

R₁ may be ##STR2##

R₂ is H, Cl, Br, F, C₁ -C₃ alkyl, --NO₂, --SO₂ CH₃, --OCH₃, --SCH₃,--CF₃, --N(CH₃)₂, --NH₂ or --CN;

R₃ is H, Cl, Br, F or CH₃ ;

R₄ is H or --CH₃ ;

R₅ is H, --CH₃ or --OCH₃ ;

Z is CH or N;

X is H, Cl, --CH₃, --OCH₃, --OCH₂ CH₃ or --OCH₂ CH₂ OCH₃ ;

Y is H; Cl; C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted with --OCH₃, --OC₂H₅, --CN, --CO₂ CH₃, --CO₂ C₂ H₅, or 1 to 3 atoms of F, Cl, Br; C₃ -C₄alkenyl; --CH₂ C.tbd.CR₁₃ where R₁₃ is H, --CH₃, --CH₂ Cl;--A--(CH₂)_(n') A₁ --(C₁ -C₃ alkyl), and n', A and A₁ are as previouslydefined.

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products that satisfy man's basic foodand fiber needs, such as rice, corn and soybeans. Compounds such as theones indicated above, are extremely effective for killing or inhibitingthe growth of undesired vegetation; such materials are commonly referredto as herbicides. The need still exists for more effective herbicides.

SUMMARY OF THE INVENTION

This invention relates to novel compounds of Formula I, agriculturallysuitable compositions containing them and their method-of-use asselective preemergent or post-emergent herbicides. ##STR3## wherein R isC₂ H₅ or CH(CH₃)₂ ; and their agriculturally suitable salts.

This invention also relates to herbicidally effective combinations ofcompounds of Formula I with compounds of Formula II ##STR4## wherein

E is H, Cl, Br, F or CF₃ ; and

R₁ is C₁ -C₄ alkyl or CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃.

This invention also relates to herbicidally effective combinations ofcompounds of Formula I with the compound of Formula III ##STR5##

Specifically preferred are:

2-[[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoicacid ethyl ester, m.p. 198°-201°; and

2-[[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoicacid isopropyl ester, m.p. 185°-187°.

DETAILED DESCRIPTION OF THE INVENTION

Compounds of Formula I are prepared by the procedure of Equation 1. Thisprocedure is well known in the art.

EQUATION 1 ##STR6## For details, one may refer to EPO Publication No.0007687 and U.S. Pat. No. 4,169,719 which are herein incorporated byreference.

Sulfonyl isocyanates of Formula a are also known in the art. Forexample, U.S. Pat. No. 4,305,884 teaches the preparation of thesecompounds.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides and can be prepared in a number of ways known to the art. Forexample, metal salts can be made by contacting compounds of Formula Iwith a solution of an alkali or alkaline earth metal salt having asufficiently basic anion (e.g., hydroxide, alkoxide, carbonate orhydroxide). Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of onecation for another. Cationic exchange can be effected by direct contactof an aqueous solution of a salt of a compound of Formula I (e.g.,alkali or quaternary amine salt) with a solution containing the cationto be exchanged. This method is most effective when the desired saltcontaining the exchanged cation is insoluble in water and can beseparated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of Formula I (e.g., an alkai metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged for that of the original salt and the desiredproduct is eluted from the column. This method is particularly usefulwhen the desired salt is water-soluble.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of Formula I with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like.

The compounds of this invention and their preparation are furtherillustrated by the following examples wherein temperatures are given indegrees centigrade and parts are by weight unless otherwise designated.

EXAMPLE 1 2-Amino-4-chloro-6-methoxypyrimidine

16.4 g 2-amino-4,6-dichloropyrimidine (purchased from Aldrich ChemicalCo., Milwaukee, WI 53201) was added to 200 ml of CH₃ OH. The mixture wascooled to 10° with an ice bath and 5.4 g of NaOCH₃ was added in portionswhile maintaining the temperature. The reaction mixture was allowed towarm to ambient temperature and then heated to reflux for two hours. Thereaction mixture was then allowed to cool to ambient temperature and itwas stirred overnight. A yellow solid was filtered and recrystallizedfrom butyl chloride. The resulting solid was chromatographed on a drycolumn of silica, and eluted with 40% EtOAchexane. The resulting yellowsolid was further purified by recrystallization from butyl chloride. 9.4g of product with m.p. 163°-166° was obtained.

EXAMPLE 22-[[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoicacid ethyl ester

To 1.0 g of 2-amino-4-chloro-6-methoxypyrimidine suspended in 25 ml ofdry CH₂ Cl₂ was added 1.53 g of ethyl 2-(isocyanatosulfonyl)benzoate(prepared by procedures taught in U.S. Pat. No. 4,305,884). The reactionmixture was stirred at ambient temperature for three days. The solventwas stripped and the product was recrystallized from butyl chloride togive a white solid with m.p. 198°-201°.

Using procedures analogous to Example 2,2-[[(4-chloro-6-methoxyprimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoicacid isopropyl ester may be prepared.

The compounds of this invention may be used in combination with othercommercial herbicides. They are particularly useful in combination withthe following herbicides.

    ______________________________________                                        Common Name                                                                              Chemical Name                                                      ______________________________________                                        amitrole   3-amino-s-triazole                                                 atrazine   2-chloro-4-(ethylamino)-6-(isopropyl-                                         amino)-s-triazine                                                  barban     4-chloro-2-butynyl m-chlorocarbanilate                             benzoylprop                                                                              N--benzoyl-N--(3,4-dichlorophenyl)-DL-                                        alaine                                                             bromacil   5-bromo-3-sec-butyl-6-methyluracil                                 bromoxynil 3,5-dibromo-4-hydroxybenzonitrile                                  butylate   S--ethyl-diisobutylthiocarbamate                                   chlortoluron                                                                             N'--(3-chloro-4-methylphenyl-N',N'--                                          dimethylurea                                                       cyanazine  2-[[4-chloro-6-(ethylamino)-s-triazin-                                        2-yl]amino]-2-methylpropionitrile                                  diallate   S--(2,3-dichloroallyl)diisopropylthio-                                        carbamate                                                          dicamba    3,6-dichloro-o-anisic acid                                         dichloroprop                                                                             2-(2,4-dichlorophenoxy)propionic acid                              diclofop   2-[4-(2,4-dichlorophenoxy)phenoxy]-                                           propanoic acid                                                     difenzoquat                                                                              1,2-dimethyl-3,5-diphenyl-1H--pyrazolium                           dinoseb    2-sec-butyl-4,6-dinitrophenol                                      diuron     3-(3,4-dichlorophenyl)-1,1-dimethylurea                            EPTC       S--ethyl-dipropylthiocarbamate                                     flamprop   N--benzoyl-N--(3-chloro-4-fluorophenyl)-DL-                                   alanine                                                            fluchloralin                                                                             N--(2-chloroethyl)-2,6-dinitro-N--propyl-4-                                   trifluoromethyl)aniline                                            fluometuron                                                                              1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)-                   urea                                                               fomesafen  5-(2-chloro-4-trifluoromethylphenoxy)-                                        N--methylsulfonyl-2-nitrobenzamide                                 fosamine   ethyl hydrogen (aminocarbonyl)phosphonate                          glyphosate N--(phosphonomethyl)glycine                                        hexazinone 3-cyclohexyl-6-(dimethylamino)-1-methyl-                                      1,3,5-triazine-2,4(1H,3H)--dione                                   ioxynil    4-hydroxy-3,5-diiodobenzonitrile                                   isoproturon                                                                              N--(4-isopropylphenyl)-N',N'--dimethylurea                         lenacil    3-cyclohexyl-6,7-dihydro-1H--cyclopenta-                                      pyrimidine-2,4(3H,5H)--dione                                       MCPA       [(4-chloro-o-tolyl)oxy]acetic acid                                 MCPB       4-[(4-chloro-o-tolyl)oxy]propionic acid                            mefluidide N--[2,4-dimethyl-5-[[(trifluoromethyl)-                                       sulfonyl]amino]phenyl]acetamide                                    methabenz- 1,3-dimethyl-3-(2-benzothiazolyl)urea                              thiazuron                                                                     methoxuron N'--(3-chloro-4-methoxyphenyl)N,N--                                           dimethylurea                                                       MSMA       monosodium methanearsonate                                         neburon    1-butyl-3-(3,4-dichlorophenyl)-1-methyl-                                      urea                                                               oryzalin   3,4-dinitro-N,N--dipropylsulfanilamide                             paraquat   1,1'-dimethyl-4,4'-bipyridinium ion                                profluralin                                                                              N--(cyclopropylmethyl)-α,α,α-trifluoro-                     2,6-dinitro-N--propyl-p-toluidine                                  propanil   3',4'-dichloropropionalide                                         siduron    1-(2-methylcyclohexyl)-3-phenylurea                                supriox    2-[1-(2,5-dimethylphenyl)ethylsulfonyl]-                                      pyridine-N--oxide                                                  terbacil   3-tert-butyl-5-chloro-6-methyluracil                               triallate  S--(2,3,3-trichloroallyl)diisopropylthio-                                     carbamate                                                          2,4-D      (2,4-dichlorophenoxy)acetic acid                                   2,4-DB     4-(2,4-dichlorophenoxy)butyric acid                                           3,4-diaryl-4-cyanobutyrates                                                   4-(6-chloroquinoxalinyl-2-oxy)phenoxy-                                        propionate C.sub.1 -C.sub.5 alkyl esters, such                                as methyl ester, butyl ester, ethyl                                           ester, pentyl ester                                                           ethoxyethoxyethyl 4-(6-chloroquinoxalin-                                      yl-2-oxy)phenoxypropionate                                                    propargyl 2-[4-(3,5-dichloropyridin-2-                                        yloxy)phenoxy]propanoate                                                      methyl 2-[4-(3-chloro-5-trifluoromethyl-                                      pyridin-2-yloxy)phenoxy]propanoate                                 oxyfluorfen                                                                              2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-                                       (trifluoromethyl)benzene                                           norflurazon                                                                              4-chloro-5-(methylamino)-2-[(3-(tri-                                          fluoro)phenyl]-3(2H)--pyridazinone                                 vernolate  S--propyl dipropylthiocarbamate                                               ethyl 5-[2-chloro-4-(trifluoromethyl)-                                        phenoxy]-2-nitrobenzoic acid                                       ______________________________________                                    

The compounds of this invention may particularly be useful incombination with the following herbicides for use as pre- orpost-emergent treatments for control of weeds in soybeans:

    ______________________________________                                        Common Name Tradename  Chemical Name                                          ______________________________________                                        acifluorfen Blazer ®                                                                             5-[2-chloro-4-(trifluoro-                                                     methyl)phenoxy]-2-ni-                                                         trobenzoic acid                                        alachlor    Lasso ®                                                                              2-chloro-2',6'-diethyl-                                                       N--(methoxymethyl)acet-                                                       anilide                                                bentazon    Basagran ®                                                                           3-isopropyl-1H--2,1,3-                                                        benzothiadiazin-4(3H)--                                                       one 2,2-dioxide                                        chloramben  Amiben ®                                                                             3-amino-2,5-dichloro-                                                         benzoic acid                                           fluazifop-  Fusilade ®                                                                           butyl 2-[4-[5-(trifluoro-                              butyl                  methyl)-2-pyridinyl-                                                          oxy]phenoxy]propanoate                                 linuron     Lorox ®                                                                              3-(3,4-dichlorophenyl)-1-                                                     methoxy-1-methylurea                                   metolachlor Dual ® 2-chloro-N--(2-ethyl-6-                                                       methylphenyl)-N--(2-                                                          methoxy-1-methylethyl)-                                                       acetamide                                              metribuzin  Lexone ®                                                                             4-amino-6-tert-butyl-3-                                                       (methylthio)-as-tri-                                                          azin-5(4H)one                                          pendimethalin                                                                             Prowl ®                                                                              N--(1-ethylpropyl)-3,4-                                                       dimethyl-2,6-dinitro-                                                         benzeneamine                                           sethoxydim  Poast ®                                                                              2-[1-(ethoxyimino)butyl]-                                                     5-[2-(ethylthio)-                                                             propyl]-3-hydroxy-2-                                                          cyclohexene-1-one                                      trifluralin Treflan ®                                                                            α,α,α-trifluoro-2,6-di-                                     nitro-N,N--dipropyl-p-                                                        toluidine                                              AC 252,214  --         2-(4,5-dihydro-4-methyl-                                                      4-(1-methylethyl)-5-                                                          oxo-1H--imidazol-2-yl)-                                                       3-quinolinecarboxylic                                                         acid                                                   FMC 57020   --         2-(2'-chlorophenyl)-                                                          methyl-4,4-dimethyl-                                                          3-isoxazolidinone                                      fomesafen   Flex ® 5-(2-chloro-4-trifluoro-                                                      methylphenoxy)-N--                                                            methylsulfonyl-2-nitro-                                                       benzamide                                              lactofen    --         1'-(carboethoxy)ethyl-5-                                                      (2-chloro-4-(trifluoro-                                                       methyl)phenoxy)-2-                                                            nitrobenzoate                                          DOWCO 453 ME           2-(4-(3-chloro-5-tri-                                                         fluoromethylpyridin-2-                                                        yloxy)phenoxy)propanoic                                                       acid, methyl ester                                     fenoxaprop ethyl                                                                          Whip ® ethyl 2-(4-(6-chloro-2-                                                       benzoxazolyloxy)phen-                                                         oxy)propanoate                                         CGA 82725   Topik ®                                                                              2-(4-(3,5-dichloropyri-                                                       din-2-yloxy)phenoxy-                                                          propanoic acid, propyn-                                                       yl ester                                               ______________________________________                                    

A particularly preferred mixture would be an effective amount of acompound of Formula I and an effective amount of a compound of FormulaII below: ##STR7## Most preferred would be a mixture with a compound ofFormula II wherein Z is Cl and R is CH₂ CH₃.

Ratios in the mixture should be 3 to 48% by weight of a compound ofFormula I and 52 to 97% by weight of a compound of Formula II.Preferably 6 to 20% of a compound of Formula I and 80 to 94% of acompound of Formula II.

The compounds of Formula II may be prepared by the process disclosed inEPO Application No. 81,302,801.6, published Dec. 30, 1981 and EPOApplication No. 82,306,769.9, published June 29, 1983.

FORMULATIONS

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). Morespecifically, they will contain these ingredients in the followingapproximate proportions:

                  TABLE I                                                         ______________________________________                                                    Active  Weight Percent*                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74      1-10                                       Oil Suspensions,                                                                             3-50     40-95      0-15                                       Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84      1-20                                       Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9   0-15                                       High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredients can, of coruse, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., New York, 1964,list surfactants and recommended uses. All formulations can containminor amounts of additives to reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration technique. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 3 Wettable Powder

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            80%                                                 carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         sodium alkylnaphthalenesulfonate                                                                        2%                                                  sodium ligninsulfonate    2%                                                  synthetic amorphous silica                                                                              3%                                                  kaolinite                 13%                                                 ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 4 Low Strength Granule

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            1%                                                  carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         N,N--dimethylformamide    9%                                                  attapulgite granules      90%                                                 (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 5 Aqueous Suspension

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                             40%                                                carbonyl]aminosulfonyl]benzoic acid isopropyl                                 ester                                                                         polyacrylic acid thickener 0.3%                                               dodecylphenol polyethylene glycol ether                                                                  0.5%                                               disodium phosphate         1%                                                 monosodium phosphate       0.5%                                               polyvinyl alcohol          1.0%                                               water                      56.7%                                              ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 6 Granule

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            80%                                                 carbonyl]aminosulfonyl]benzoic acid isopropyl                                 ester                                                                         wetting agent              1%                                                 crude ligninsulfonate salt (containing                                                                  10%                                                 5-20% of the natural sugars)                                                  attapulgite clay           9%                                                 ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 7 High Strength Concentrate

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                             99%                                                carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         silica aerogel            0.5%                                                synthetic amorphous silica                                                                              0.5%                                                ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 8 Wettable Powder

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                             90%                                                carbonyl]aminosulfonyl]benzoic acid isopropyl                                 ester                                                                         dioctyl sodium sulfosuccinate                                                                           0.1%                                                synthetic fine silica     9.9%                                                ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 9 Wettable Powder

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            40%                                                 carbonyl]aminosulfonyl]benzoic acid isopropyl                                 ester                                                                         sodium ligninsulfonate    20%                                                 montmorillonite clay      40%                                                 ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 10 Wettable Powder

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            50%                                                 carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         sodium alkylnaphthalenesulfonate                                                                         2%                                                 low viscosity methyl cellulose                                                                           2%                                                 diatomaceous earth        46%                                                 ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 11 Granule

    ______________________________________                                        Wettable Powder of Example 10                                                                         5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing ≈25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 12 Extruded Pellet

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            25%                                                 carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         anhydrous sodium sulfate  10%                                                 crude calcium ligninsulfonate                                                                            5%                                                 sodium alkylnaphthalenesulfonate                                                                         1%                                                 calcium/magnesium bentonite                                                                             59%                                                 ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 13 Oil Suspension

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            25%                                                 carbonyl]aminosulfonyl]benzoic acid isopropyl                                 ester                                                                         polyoxyethylene sorbitol hexaoleate                                                                      5%                                                 highly aliphatic hydrocarbon oil                                                                        70%                                                 ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 14 Wettable Powder

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            20%                                                 carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         sodium alkylnaphthalenesulfonate                                                                        4%                                                  sodium ligninsulfonate    4%                                                  low viscosity methyl cellulose                                                                          3%                                                  attapulgite               69%                                                 ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 15 Oil Suspension

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            35%                                                 carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         blend of polyalcohol carboxylic                                                                          6%                                                 esters and oil soluble petroleum                                              sulfonates                                                                    xylene                    59%                                                 ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 16 Dust

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            10%                                                 carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         attapulgite               10%                                                 Pyrophyllite              80%                                                 ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer-mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

EXAMPLE 17 Emulsifiable Concentrate

    ______________________________________                                        2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-                                                            20%                                                 carbonyl]aminosulfonyl]benzoic acid ethyl                                     ester                                                                         chlorobenzene             74%                                                 sorbitan monostearate and polyoxyethylene                                                                6%                                                 condensates thereof                                                           ______________________________________                                    

The ingredients are combined and stirred to produce a solution which canbe emulsified in water for application.

UTILITY

The compounds of the present invention have high herbicidal properties.They have utility for broadspectrum pre- and/or post-emergence weedcontrol, in particular selective weed control in soybeans.

The rates of application for the compounds of the invention aredetermined by a number of factors, including the types of weeds to becontrolled, weather and climate, formulations selected, mode ofapplication, amount of foliage present, etc. In general terms, thesubject compounds should be applied at levels of around 0.002 to 1kg/ha, the lower rates being suggested for use on lighter soils and/orthose having a low organic matter content, or for situations where onlyshort-term persistence is required.

The compounds of the invention may be used in combination with any othercommercial herbicide, examples of which are those of the triazine,triazole, uracil, urea, amide, diphenylether, carbamate and bipyridyliumtypes.

As mentioned previously, compounds of this invention may also be used incombination with herbicides such as those of Formula II. Compound 3 isrepresentative of this class of compounds, and may be used at rates of0.035 to 1 kg/ha depending upon the above factors. Such combinations orsplit applications may be useful in obtaining both grass and broadleafweed control in soybeans.

The herbicidal properties of the subject compounds were discovered in anumber of greenhouse tests. The test procedures and results follow.

TEST A

Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia),morningglory (Ipomoea sp.), cocklebur (Xanthium pensylvanicum), sorghum,corn, soybean, sugar beet, rice, wheat and purple nutsedge (Cyperusrotundus) tubers were planted and treated pre-emergence with the testchemicals dissolved in a non-phytotoxic solvent. At the same time, thesecrop and weed species, along with cotton and bush bean, were treatedwith a soil/foliage application. At the time of treatment, the plantsranged in height from 2 to 18 cm. Treated plants and controls weremaintained in a greenhouse for sixteen days, after which all specieswere compared to controls and visually rated for response to treatment.The ratings, summarized in Table A, are based on a numerical scaleextending from 0=no injury, to 10=complete kill. The accompanyingdescriptive symbols have the following meanings:

C=chlorosis/necrosis;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effects;

U=unusual pigmentation; and

6Y=abscised buds or flowers.

The data indicate the high herbicidal activity of the compounds of theinvention and their utility for selective pre-emergence weed control insoybeans. ##STR8##

                  TABLE A                                                         ______________________________________                                                           Cmpd. 1   Cmpd. 2                                          Rate kg/ha         0.05      0.05                                             ______________________________________                                        POST-EMERGENCE                                                                Bush bean          9C        9C                                               Cotton             2C,9G     3C,3H,9G                                         Morningglory       10C       9C                                               Cocklebur          10C       9C                                               Sicklepod          9C        9C                                               Nutsedge           9C        9G                                               Crabgrass          2C,4G     2C,5G                                            Barnyardgrass      5C,9H     3C,9H                                            Wild Oats          6C,9G     8G                                               Wheat              6C,9G     2C,9G                                            Corn               5U,9C     2C,8H                                            Soybean            4C,9G     2C,6G                                            Rice               5C,9G     5C,9G                                            Sorghum            5C,9G     3C,9G                                            Sugar beet         5C,9G     4C,9G                                            PRE-EMERGENCE                                                                 Morningglory       9C        9C                                               Cocklebur          --        9H                                               Sicklepod          9G        8G                                               Nutsedge           10E       10E                                              Crabgrass          0         0                                                Barnyardgrass      2C,9H     4C,9H                                            Wild Oats          2C,8G     2C,6G                                            Wheat              9H        8G                                               Corn               2C,9G     1C,9G                                            Soybean            0         1C                                               Rice               10E       10E                                              Sorghum            7C,9H     2C,9H                                            Sugar beet         10E       10E                                              ______________________________________                                    

TEST B

Two plastic bulb pans were filled with fertilized and limed Woodstownsandy loam. One pan was planted with corn, sorghum, Kentucky bluegrassand several grassy weeds. The other pan was planted with cotton,soybeans, purple nutsedge (Cyperus rotundus), and several broadleafweeds. The following grassy and broadleaf weeds were planted: crabgrass(Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wildoats (Avena fatua), johnsongrass (Sorghum halepense), dallisgrass(Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass(Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthiumpensylvanicum), morningglory (Ipomoea hederacea), sicklepod (Cassiaobtusifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti),and jimsonweed (Datura stramonium). A 12.5 cm diameter plastic pot wasalso filled with prepared soil and planted with rice and wheat. Another12.5 cm pot was planted with sugar beets. The above four containers weretreated pre-emergence with the test compounds of the invention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table B. Note that the compounds are useful as pre-emergencetreatments for weed control in soybeans.

                                      TABLE B                                     __________________________________________________________________________    PRE-EMERGENCE ON                                                              WOODSTOWN SANDY LOAM                                                                  Compound 1               Compound 2                                   Rate kg/ha                                                                            0.00175                                                                           0.0035                                                                            0.015                                                                             0.030                                                                              0.060                                                                             0.500                                                                             0.00175                                                                            0.0035                                                                            0.015                                                                             0.030                                                                             0.060                                                                              0.120                                                                             0.500              __________________________________________________________________________    Crabgrass                                                                             5G  5G  3G  6G   6G  9G  2G   2G  0   2G  3G   5G  8G                 Barnyardgrass                                                                         6G  6G  9G  9G,9C                                                                              9G,9C                                                                             10C 4G   5G  6G  7G  8G   8G  9G,9C              Sorghum 7G  9G,9C                                                                             10C 10C  10C 10C 5G   7G  10C 10C 10C  10C 10C                Wild Oats                                                                             3G  4G  8G  8G,3C                                                                              8G,5C                                                                             9G,9C                                                                             2G   3G  4G  5G  7G   7G  9G                 Johnsongrass                                                                          0   0   8G  8G   8G  9G,9C                                                                             0    0   7G  7G  8G   8G  9G,9C              Dallisgrass                                                                           0   2G  5G  7G   8G  9G  0    0   4G  5G  5G   6G  9G                 Giant foxtail                                                                         0   2G  6G  7G   7G  9G  2G   2G  4G  5G  8G   9G  9G                 Ky. bluegrass                                                                         0   2G  9G  9G   9G,9C                                                                             10C 2G   5G  8G  9G  9G   9G  10C                Cheatgrass                                                                            8G  9G  9G,9C                                                                             10C  10C 10C 7G   8G  9G,9C                                                                             9G,9C                                                                             9G,9C                                                                              10C 10C                Sugar beets                                                                           9G  9G  10C 10C  10C 10C 9G   9G  9G  9G  9G,9C                                                                              10C 10C                Corn    2G  3G  6G  8G,5H                                                                              8G,7H                                                                             10C 0    2G  4G  3G  6G   8G,5H                                                                             10C                Mustard 9G  9G  9G,9C                                                                             9G,9C                                                                              10C 10C 9G   9G  9G,9C                                                                             9G,9C                                                                             10C  10C 10C                Cocklebur                                                                             7G  8G  9G,3H                                                                             9G,5H                                                                              9G,7H                                                                             9G,9C                                                                             7G   8G  9G,5H                                                                             9G,5H                                                                             9G,7H                                                                              9G,7H                                                                             9G,9C              Pigweed --  --  --  --   --  --  --   --  --  --  --   --  --                 Nutsedge                                                                              10C 10C 10C 10C  10C 10C 8G   9G  10C 10C 10C  10C 10C                Cotton  8G  8G  9G  9G   9G  10C 6G   8G  8G  8G  8G   9G  9G,9C              Morningglory                                                                          5G  7G  9G  9G   9G  9G,9C                                                                             5G   7G  9G  9G  9G   9G  9G,9C              Sicklepod                                                                             4G  6G  8G  9G   9G  9G,9C                                                                             0    4G  2G  5G  8G   8G  9G                 Teaweed 0   4G  8G  9G   9G  9G,9C                                                                             0    0   8G  8G  9G   9G  9G                 Velvetleaf                                                                            4G  7G  8G  9G   9G  9G,9C                                                                             0    5G  7G  8G  9G   9G  9G,9C              Jimsonweed                                                                            7G  9G,9C                                                                             9G,9C                                                                             9G,9C                                                                              9G,9C                                                                             9G,9C                                                                             6G   8G  9G  9G  9G,9C                                                                              9G,9C                                                                             9G,9C              Soybean 0   0   2G  2G   3G  7G  0    0   0   0   2G   2G  6G                 Rice    9G  10C 10C 10C  10C 10C 9G   9G  10C 10C 10C  10C 10C                Wheat   4G  7G  3G  6G   8G  9G  4G   6G  5G  4G  5G   6G  8G                 __________________________________________________________________________

TEST C

The test chemicals, dissolved in a non-phytotoxic solvent, were appliedin an overall spray to the foliage and surrounding soil of selectedplant species. One day after treatment, plants were observed for rapidburn injury. Approximately fourteen days after treatment, all specieswere visually compared to untreated controls and rated for response totreatment. The rating system was as described previously for Test A. Thedata are presented in Table C.

All plant species were seeded in Woodstown sandy loam soil and grown ina greenhouse. The following species were grown in soil contained inplastic pots (25 cm diameter by 13 cm deep): soybeans, cotton, alfalfa,corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania(Sesbania exaltata), sicklepod (Cassia obtusifolia), morningglory(Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthiumpensylvaicum), crabgrass (Digitaria sp.), nutsedge (Cyperus rotundus),barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii)and wild oats (Avena fatua). The following species were grown in soil ina paper cup (12 cm diameter by 13 cm deep): sunflower, sugar beets, andmustard. All plants were sprayed approximately 14 days after planting.Additional plant species are sometimes added to this standard test inorder to evaluate unusual selectivity.

The compounds tested by this procedure are useful for the post-emergencecontrol of weeds in soybeans.

                  TABLE C                                                         ______________________________________                                        Over-the-Top Soil/Foliage Treatment                                                  Compound 1    Compound 2                                               Rate kg/ha                                                                             .004    .016    .063  .004  .016  .063                               ______________________________________                                        Soybeans 0       5G      9G    0     7G    8G,6C                              Velvetleaf                                                                             9G,4C   10C     10C   9G    10C   10C                                Sesbania 10C     10C     10C   10C   10C   10C                                Sicklepod                                                                              7G      10C     10G,  6G,4C 10C   10G,                                                        4C                4C                                 Cotton   8G      10C     10C   10C   10C   10C                                Morningglory                                                                           9G,2C   10C     9G,9C 10C   9G,8C 10C                                Alfalfa  5G      10C     9G,8C 10C   8G,2C 10C                                Jimsonweed                                                                             8G      9G,2C   9G    8G    10C   10C                                Cocklebur                                                                              9G,1H   8G,1H   9G    --    9G    10C                                Sunflower                                                                              10C     10C     10C   9G,9C 10C   10C                                Mustard  9G,5C   10C     10C   9G,6C 9G,6C 9G,4C                              Sugar beets                                                                            10C     10C     10C   9G    10C   10C                                Corn     2G,2C   5G,1U   7G    1C    2G,2C 5G,2H                              Crabgrass                                                                              0       0       0     0     2G    0                                  Rice     8G,2C   9G,8C   9G,8C 6G    9G,7C 9G,4C                              Nutsedge 9G      8G      8G,6C 7G    7G,6C 7G                                 Barnyard-                                                                              6G      8G,6C   9G,6C 5G    7G    8G,6C                              grass                                                                         Wheat    4G      8G      9G    0     6G    8G                                 Giant foxtail                                                                          6G      7G      8G    3G    6G    9G                                 Wild Oats                                                                              2G      7G      8G    0     4G    7G                                 Sorghum  6G      8G,1U   9G,2U 7G    7G,2U 7G,2U                              Johnsongrass                                                                           5G      8G,1U   8G,1U 5G    7G    7G,4U                              Field    0       8G      8G    6G    4G    8G                                 Bindweed                                                                      ______________________________________                                    

TEST D

Four inch round pots were filled with Woodstown soil and various weedseeds were sown in separate pots. The pots containing the seeds wereplaced in the greenhouse and watered as needed for good plant growth. Inaddition, they were fertilized once with 10-10-10 Peter's solution.After about 3 weeks depending on species, when the plants were in the4-6 true leaf stage, they were sprayed with solutions of Compound 1,Compound 3 or both using a track sprayer calibrated to deliver 60 g.p.a.of the spray solution containing 0.1% X-77 surfactant. The plants werereplaced in the greenhouse and watered as needed for optimum growth forabout 3 weeks. They were then evaluated for percent weed control where0=no control and 100=complete kill. The following weeds were in thetest. Barnyardgrass (Echinochloa crusgalli), giant foxtail (Setariafaberi), velvetleaf (Abutilon theophrasti), hemp sesbania (Sesbaniaexaltata), sicklepod (Cassia Obtusifolia), kochia (Kochia scoparia) andRussian thistle (Salsola kali ). The data are summarized in Table D.

                  TABLE D                                                         ______________________________________                                                Rate (kg a.i./ha)                                                     ______________________________________                                        Test 1                                                                        Compound 3                                                                              1/16     1/32    1/64   1/128 1/256                                 Compound 2                                                                              1/64     1/128   1/256  1/512 1/1024                                Barnyardgrass                                                                           95       95      90     70    50                                    Giant Foxtail                                                                           100      100     99     80    50                                    Velvetleaf                                                                              100      99      90     90    90                                    Hemp sesbania                                                                           100      100     100    100   90                                    Sicklepod 95       95      95     60    60                                    Kochia    30       30       0      0     0                                    Russian thistle                                                                         20       20       0      0     0                                    Test 2                                                                        Compound 3                                                                              1/16     1/32    1/64   1/128 1/256                                 Compound 2                                                                              1/64     1/128   1/256  1/512 1/1024                                Barnyardgrass                                                                           95       90      80     80    50                                    Giant Foxtail                                                                           99       99      90     70    50                                    Velvetleaf                                                                              100      100     100    50    50                                    Hemp sesbania                                                                           100      100     100    90    100                                   Sicklepod 95       100     85     40    40                                    Kochia    60       50      30      0     0                                    Russian thistle                                                                         70       50       0      0     0                                    Test 3                                                                        Compound 3                                                                               0        0       0      0     0                                    Compound 2                                                                              1/64     1/128   1/256  1/512 1/1024                                Barnyardgrass                                                                             0       0       0      0     0                                    Giant Foxtail                                                                            0        0       0      0     0                                    Velvetleaf                                                                              100      99      99     80    80                                    Hemp sesbania                                                                           100      100     100    90    85                                    Sicklepod 95       95      90     70    60                                    Kochia    50       40      20      0     0                                    Russian thistle                                                                         90        0       0      0     0                                    Test 4                                                                        Compound 3                                                                              1/16     1/32    1/64   1/128 1/256                                 Compound 2                                                                               0        0       0      0     0                                    Barnyardgrass                                                                           98       95      90     70    50                                    Giant Foxtail                                                                           100      100     100    80    60                                    Velvetleaf                                                                               0        0       0      0     0                                    Hemp sesbania                                                                            0        0       0      0     0                                    Sicklepod  0        0       0      0     0                                    Kochia     0        0       0      0     0                                    Russian thistle                                                                          0        0       0      0     0                                    ______________________________________                                    

What is claimed is:
 1. A compound of the formula: ##STR9## wherein R isC₂ H₅ or CH(CH₃)₂ ; and their agriculturally suitable salts.
 2. Thecompound of claim 1 which is2-[[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoicacid ethyl ester.
 3. The compound of claim 1 which is2-[[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoicacid isopropyl ester.
 4. A mixture of an herbicidally effective amountof a compound of claim 1 with an herbicidally effective amount of acompound of the formula: ##STR10## wherein E is H, Cl, Br, F or CF₃ ;andR₁ is C₁ -C₄ alkyl or CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃.
 5. A mixture of aneffective amount of the compound of claim 2 with an effective amount ofthe compound of claim 4 wherein E is Cl and R is CH₂ CH₃.
 6. A mixtureof an effective amount of the compound of claim 2 with an effectiveamount of the compound of the formula: ##STR11##
 7. A compositionsuitable for controlling the growth of undesired vegetation whichcomprises an effective amount of a compound of claim 1 and at least oneof the following: surfactant, solid or liquid diluent.
 8. A compositionsuitable for controlling the growth of undesired vegetation whichcomprises an effective amount of the compound of claim 2 and at leastone of the following: surfactant, solid or liquid diluent.
 9. Acomposition suitable for controlling the growth of undesired vegetationwhich comprises an effective amount of the compound of claim 3 and atleast one of the following: surfactant, solid or liquid diluent.
 10. Amixture suitable for controlling the growth of undesired vegetationwhich comprises an effective amount of a mixture of claim 4 and at leastone of the following: surfactant, solid or liquid diluent.
 11. A mixturesuitable for controlling the growth of undesired vegetation whichcomprises an effective amount of a mixture of claim 5 and at least oneof the following: surfactant, solid or liquid diluent.
 12. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound ofclaim
 1. 13. A method for controlling the growth of undesired vegetationwhich comprises applying to the locus to be protected an effectiveamount of the compound of claim
 2. 14. A method for controlling thegrowth of undesired vegetation which comprises applying to the locus tobe protected an effective amount of the compound of claim
 3. 15. Amethod for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of amixture of claim
 4. 16. A method for controlling the growth of undesiredvegetation which comprises applying to the locus to be protected aneffective amount of a mixture of claim
 5. 17. A method for controllingthe growth of undesired vegetation found growing in conjunction withsoybeans which comprises applying to the locus to be protected aneffective amount of the compound of claim
 2. 18. A method forcontrolling the growth of undesired vegetation found growing inconjunction with soybeans which comprises applying to the locus to beprotected an effective amount of the mixture of claim 5.